EP3155167B1 - In-situ-gummiertes kabel mit einer gummierzusammensetzung mit einem korrosionsinhibitor - Google Patents

In-situ-gummiertes kabel mit einer gummierzusammensetzung mit einem korrosionsinhibitor Download PDF

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Publication number
EP3155167B1
EP3155167B1 EP15731535.9A EP15731535A EP3155167B1 EP 3155167 B1 EP3155167 B1 EP 3155167B1 EP 15731535 A EP15731535 A EP 15731535A EP 3155167 B1 EP3155167 B1 EP 3155167B1
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Prior art keywords
situ
cable
group
independently
composition
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English (en)
French (fr)
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EP3155167A2 (de
Inventor
Lionel BELIN
Nathalie Salgues
Sébastien Noel
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Compagnie Generale des Etablissements Michelin SCA
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Compagnie Generale des Etablissements Michelin SCA
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • B60C9/0007—Reinforcements made of metallic elements, e.g. cords, yarns, filaments or fibres made from metal
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/06—Ropes or cables built-up from metal wires, e.g. of section wires around a hemp core
    • D07B1/0606—Reinforcing cords for rubber or plastic articles
    • D07B1/0613—Reinforcing cords for rubber or plastic articles the reinforcing cords being characterised by the rope configuration
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/06—Ropes or cables built-up from metal wires, e.g. of section wires around a hemp core
    • D07B1/0606—Reinforcing cords for rubber or plastic articles
    • D07B1/062—Reinforcing cords for rubber or plastic articles the reinforcing cords being characterised by the strand configuration
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/06—Ropes or cables built-up from metal wires, e.g. of section wires around a hemp core
    • D07B1/0606—Reinforcing cords for rubber or plastic articles
    • D07B1/062—Reinforcing cords for rubber or plastic articles the reinforcing cords being characterised by the strand configuration
    • D07B1/0626—Reinforcing cords for rubber or plastic articles the reinforcing cords being characterised by the strand configuration the reinforcing cords consisting of three core wires or filaments and at least one layer of outer wires or filaments, i.e. a 3+N configuration
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/06—Ropes or cables built-up from metal wires, e.g. of section wires around a hemp core
    • D07B1/0606—Reinforcing cords for rubber or plastic articles
    • D07B1/062—Reinforcing cords for rubber or plastic articles the reinforcing cords being characterised by the strand configuration
    • D07B1/0633—Reinforcing cords for rubber or plastic articles the reinforcing cords being characterised by the strand configuration having a multiple-layer configuration
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/06—Ropes or cables built-up from metal wires, e.g. of section wires around a hemp core
    • D07B1/0606—Reinforcing cords for rubber or plastic articles
    • D07B1/0646—Reinforcing cords for rubber or plastic articles comprising longitudinally preformed wires
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/16—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics
    • D07B1/165—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics characterised by a plastic or rubber inlay
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • B60C9/0007—Reinforcements made of metallic elements, e.g. cords, yarns, filaments or fibres made from metal
    • B60C2009/0021—Coating rubbers for steel cords
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2201/00—Ropes or cables
    • D07B2201/20—Rope or cable components
    • D07B2201/2001—Wires or filaments
    • D07B2201/2002—Wires or filaments characterised by their cross-sectional shape
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2201/00—Ropes or cables
    • D07B2201/20—Rope or cable components
    • D07B2201/2015—Strands
    • D07B2201/2046—Strands comprising fillers
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2201/00—Ropes or cables
    • D07B2201/20—Rope or cable components
    • D07B2201/2047—Cores
    • D07B2201/2052—Cores characterised by their structure
    • D07B2201/2059—Cores characterised by their structure comprising wires
    • D07B2201/2061—Cores characterised by their structure comprising wires resulting in a twisted structure
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2201/00—Ropes or cables
    • D07B2201/20—Rope or cable components
    • D07B2201/2047—Cores
    • D07B2201/2052—Cores characterised by their structure
    • D07B2201/2059—Cores characterised by their structure comprising wires
    • D07B2201/2062—Cores characterised by their structure comprising wires comprising fillers
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2201/00—Ropes or cables
    • D07B2201/20—Rope or cable components
    • D07B2201/2047—Cores
    • D07B2201/2052—Cores characterised by their structure
    • D07B2201/2065—Cores characterised by their structure comprising a coating
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2201/00—Ropes or cables
    • D07B2201/20—Rope or cable components
    • D07B2201/2075—Fillers
    • D07B2201/2077—Fillers having an anti-corrosive function
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2201/00—Ropes or cables
    • D07B2201/20—Rope or cable components
    • D07B2201/2075—Fillers
    • D07B2201/2079—Fillers characterised by the kind or amount of filling
    • D07B2201/208—Fillers characterised by the kind or amount of filling having an open structure
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2201/00—Ropes or cables
    • D07B2201/20—Rope or cable components
    • D07B2201/2075—Fillers
    • D07B2201/2079—Fillers characterised by the kind or amount of filling
    • D07B2201/2081—Fillers characterised by the kind or amount of filling having maximum filling
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2201/00—Ropes or cables
    • D07B2201/20—Rope or cable components
    • D07B2201/2075—Fillers
    • D07B2201/2082—Fillers characterised by the materials used
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2201/00—Ropes or cables
    • D07B2201/20—Rope or cable components
    • D07B2201/2095—Auxiliary components, e.g. electric conductors or light guides
    • D07B2201/2097—Binding wires
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2401/00—Aspects related to the problem to be solved or advantage
    • D07B2401/20—Aspects related to the problem to be solved or advantage related to ropes or cables
    • D07B2401/202—Environmental resistance
    • D07B2401/2025—Environmental resistance avoiding corrosion

Definitions

  • the invention relates to a monotoron cable gummed in situ, a multi-strand cable gummed in situ and the use of such cables for the reinforcement of a semi-finished rubber product and a tire comprising such cables.
  • a radial tire comprises in known manner a tread, two inextensible beads, two sidewalls connecting the beads to the tread and a belt, or crown reinforcement, disposed circumferentially between the carcass reinforcement and the tread.
  • the carcass and / or crown reinforcement is constituted in known manner by at least one ply (or "layer") of rubber reinforced by reinforcement elements such as cables, generally of the metal type in the case of tires for industrial vehicles carrying heavy loads.
  • monotoron metal cables consist of a core layer or core and one or more layers of concentric son disposed around this core.
  • the most used three-layer cables are essentially M + N + P construction cables, formed of a core of M wire (s), M varying from 1 to 4, surrounded by an intermediate layer of N wires, N typically ranging from 3 to 12, itself surrounded by an outer layer of P son, P typically ranging from 8 to 20, the assembly may be optionally shrunk by an outer hoop thread wound helically around the outer layer.
  • Multistrand metal cables comprising several strands as described above are also used.
  • these metal cables are subjected, particularly in the case of the carcass reinforcement, to significant stresses during the rolling of the tires, in particular to repeated bending or variations of curvature inducing at the level of the threads of friction, in particular as a result of the contacts between adjacent layers, and therefore wear, as well as fatigue; they must therefore have a high resistance to phenomena known as "fatigue-fretting".
  • crown reinforcement a heavy industrial vehicle tire, especially a civil engineering vehicle, is subjected to numerous attacks. Indeed, the rolling of this type of tire is usually done on a rough surface sometimes leading to perforations of the tread. These perforations allow the entry of corrosive agents, for example air and water, which oxidize the metal reinforcement elements of the crown reinforcement, in particular top plies, and significantly reduce the life of the tire.
  • the reinforcing elements are impregnated as far as possible by the rubber, that this material penetrates into all the spaces between the wires and / or the strands constituting the cables. Indeed, if this penetration is insufficient, then empty channels or capillaries are formed, along and inside the cables, and corrosive agents such as water or even oxygen in the air, likely to to enter the tires for example as a result of cuts in their tread, walk along these empty channels.
  • the presence of this moisture plays an important role in causing corrosion and accelerating the degradation processes above (so-called phenomena of "fatigue-corrosion" and aggression of the summit), compared to use in a dry atmosphere.
  • the demand WO 2005/071157 has proposed three-layer construction cables 1 + M + N, in particular of construction 1 + 6 + 12, one of the essential characteristics is that a sheath consisting of a rubber composition, called scrub, covers at least the intermediate layer consisting of M son, the core (or unit wire) of the cable may itself be covered or not rubber.
  • a sheath consisting of a rubber composition called scrub
  • the cable has excellent fatigue-fretting endurance and resistance to aggression properties that are significantly improved over the cables of the prior art. The longevity of the tires and that of their carcass reinforcement and / or crown are thus very significantly improved.
  • a corrosion inhibitor makes it possible, on the one hand, to prevent the action of corrosive agents by forming a protective film around the metallic reinforcing element and, on the other hand, by adsorption on the metallic reinforcing element, to slow or even stop the corrosive action of corrosive agents on and within the metal reinforcing element.
  • the object of the invention is to provide a cable gummed in situ with a rubber scrub composition comprising an effective and environmentally neutral corrosion inhibitor.
  • the rubber scrub composition according to the invention makes it possible to reduce or even eliminate the risk of corrosion of the wire rope.
  • adding a compound of formula I into the rubber composition disposed between the inner layer of the cable and the outer layer of the cable reduces the amount of compound while achieving a similar anticorrosive effect, or better than when said compound is disposed in the adjacent rubber calendering composition.
  • the compounds of formula (I) or a salt thereof capture corrosive agents before they reach the yarns protected by the scrubbing composition.
  • the composition also makes it possible to limit the corrosive action of the corrosive agents on the yarns.
  • the compounds of formula (I) or a salt thereof are carried by the corrosive agent, for example water, to the son where they adsorb on an outer surface of the son that the scrub composition protects and block the action of corrosive agents.
  • the compounds of formula (I) or a salt thereof are relatively neutral in the environment.
  • the rubber composition can be in raw or vulcanized form.
  • the son are coated with a layer of copper or brass which, among other things, improves the adhesion of the rubber to the wire by sulphidation of this layer during cooking.
  • the compounds of formula (I) or a salt of this compound do not inhibit this sulphidation and therefore do not interfere with adhesion between the metal reinforcing element and the rubber composition.
  • the compound of formula (I) is N, N-bis (phosphonomethyl) glycine.
  • ETMP ethylenediamine tetra (methylene phosphonic acid)
  • DTPMP diethylenetriamine penta (methylene phosphonic acid)
  • the composition comprises at least 0.1 pce inclusive of the compound of formula (I) and / or salts thereof.
  • the composition comprises at most 2 pce inclusive, preferably at most 1 pce inclusive and more preferably at most 0.7 pce inclusive of the compound of formula (I) and / or salt thereof.
  • the rubber composition is present in each of the capillaries located between the one or more internal thread (s) of the inner layer and the outer threads (N3) of the outer layer.
  • the cable further comprises an intermediate layer of the cable comprising N2 intermediate wires spirally wound around the inner layer of the cable, the outer N3 son of the outer layer of the cable being wound helically around the layer intermediate cable.
  • the rubber composition is present in each of the capillaries located between the inner thread (s) N1 (s) of the inner layer and the N2 intermediate son of the intermediate layer.
  • the rubber composition is present in each of the capillaries located between the intermediate thread N2 of the intermediate layer and the external N3 son of the outer layer.
  • the invention also relates to a multi-strand cable gummed in situ, comprising at least strand being a monotoron cable gummed in situ according to the invention.
  • the invention also relates to the use of a monotoron cable gummed in situ according to the invention or a multi-strand cable gummed in situ according to the invention for the reinforcement of an article or semi-finished product of rubber, for example a tire.
  • the invention furthermore relates to a tire comprising a monotoron cable gummed in situ according to the invention or to a multi-strand cable gummed in situ according to the invention.
  • the term gummed cable in situ in the sense of the invention a cable gummed from the inside, during its manufacture, so in the raw state of manufacture, by a rubber composition called scrubbing.
  • scrubbing a rubber composition formed by the adjacent strands or strands is filled, at least in part (so continuous or not along the axis of the cable), by the scrub composition such that for any cable length of 2 cm, each capillary comprises at least one rubber stopper.
  • the invention relates to a monotoron cable gummed in situ C comprising at least one inner layer of the cable CT1 and an outer layer of the cable CT3.
  • the inner layer of the cable CT1 comprises N1 internal wire (s) with N1 greater than or equal to 1.
  • the outer layer of the cable CT3 comprises N3 external wires wound helically around the inner layer of the cable CT1.
  • the inner layer CT1 may comprise one or more wires (i.e. N1 varies from 1 to 3).
  • the outer layer CT3 may comprise from ten to fourteen threads (i.e., N3 ranges from 5 to 7).
  • the cable according to the invention is gummed in situ and therefore comprises a so-called scrubber rubber composition disposed between the inner layer of the cable CT1 and the outer layer of the cable CT3.
  • the rubber (or indistinctly "elastomer”, both of which are considered synonymous) of the scrubbing composition is preferably a diene elastomer, that is to say by definition an elastomer derived at least in part (that is, ie a homopolymer or a copolymer) of monomer (s) diene (s) (ie, monomer (s) carrier (s) of two carbon-carbon double bonds, conjugated or not).
  • the diene elastomer of the composition is chosen from the group of diene elastomers consisting of polybutadienes (BR), synthetic polyisoprenes (IR) and natural rubber (NR), butadiene copolymers, isoprene copolymers and mixtures of these elastomers.
  • BR polybutadienes
  • IR synthetic polyisoprenes
  • NR natural rubber
  • Such copolymers are more preferably selected from the group consisting of butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR), isoprene-copolymers of butadiene-styrene (SBIR) and mixtures of such copolymers.
  • SBR butadiene-styrene copolymers
  • BIR isoprene-butadiene copolymers
  • SIR isoprene-styrene copolymers
  • SBIR isoprene-copolymers of butadiene-styrene
  • compositions may contain a single diene elastomer or a mixture of several diene elastomers, the diene elastomer or elastomers that may be used in combination with any type of synthetic elastomer other than diene, or even with polymers other than elastomers, for example polymers thermoplastics.
  • the composition comprises a reinforcing filler.
  • reinforcing filler When a reinforcing filler is used, it is possible to use any type of reinforcing filler known for its ability to reinforce a rubber composition that can be used for the manufacture of tires, for example an organic filler such as carbon black, a reinforcing inorganic filler such as than silica, or a blend of these two types of filler, including a blend of carbon black and silica.
  • an organic filler such as carbon black
  • a reinforcing inorganic filler such as than silica
  • silica a reinforcing inorganic filler
  • a blend of these two types of filler including a blend of carbon black and silica.
  • carbon blacks are suitable all the carbon blacks conventionally used in tires (so-called pneumatic grade blacks). For example, mention will be made more particularly of reinforcing carbon blacks of the 100, 200 or 300 series (ASTM grades).
  • any inorganic or mineral filler (regardless of its color and origin (natural or synthetic), also called “white” filler, “clear” filler or “non-black filler” as opposed to carbon black, capable of reinforcing on its own, without any other means than an intermediate coupling agent, a rubber composition intended for the manufacture of tires, in other words, capable of replacing, in its reinforcing function, a conventional carbon black of pneumatic grade,
  • a filler is generally characterized, in a known manner, by the presence of hydroxyl groups (-OH) on its surface.
  • the physical state under which the reinforcing inorganic filler is present is indifferent, whether in the form of powder, micro-beads, granules, beads or any other suitable densified form.
  • the term "reinforcing inorganic filler” also means mixtures of different fillers. reinforcing inorganic, in particular highly dispersible siliceous and / or aluminous fillers as described below.
  • Suitable reinforcing inorganic fillers are mineral fillers of the siliceous type, in particular silica (SiO 2), or aluminous type, in particular alumina (Al 2 O 3).
  • the silica used may be any reinforcing silica known to those skilled in the art, especially any precipitated or pyrogenated silica having a BET surface and a CTAB specific surface both less than 450 m 2 / g, preferably from 30 to 400 m 2 / g.
  • HDS highly dispersible precipitated silicas
  • an at least bifunctional coupling agent is used in known manner to ensure a sufficient chemical and / or physical connection between the inorganic filler ( surface of its particles) and the diene elastomer, in particular organosilanes or bifunctional polyorganosiloxanes.
  • total reinforcing filler carbon black and / or reinforcing inorganic filler such as silica
  • the content of total reinforcing filler is within a range from 5 to 120 phr inclusive, more preferably 5 to 70 phr inclusive and more preferably 5 to 60 inclusive. pce terminals included.
  • carbon black may also be used in blending with other reinforcing fillers and in particular reinforcing inorganic fillers as described above, and in particular silica. It will thus be possible to use a single silica or a blend of several different silicas.
  • an inorganic filler for example silica
  • its content is within a range from 0 to 70 phr included terminals, preferably from 0 to 60 phr. included, in particular also from 5 to 70 pce inclusive terminals, and even more preferably this proportion varies from 5 to 60 pce included terminals.
  • the scrubbing composition comprises a reinforcing filler comprising predominantly by weight of the silica and more preferably comprising only silica.
  • a reinforcing filler comprising predominantly by weight of the silica and more preferably comprising only silica.
  • the proportion by weight of silica is greater than the proportion by weight of the rest of the other reinforcing fillers of the composition, whether these fillers are organic, for example carbon black, or inorganic.
  • the scrubbing composition comprises at least 30 pce inclusive and preferably at least 40 pce included silica terminal.
  • the scrub composition comprises various additives.
  • the scrubbing compositions may also comprise all or part of the usual additives usually used in elastomer compositions intended for the manufacture of tires, for example plasticizers or extension oils, whether the latter are aromatic or non-aromatic in nature.
  • X 3 represents -COOH, -CO-NH-OH, -SOOH, -PO (OR) (R ') or -PO (OR) (OR') with R, R 'independently representing one of the other hydrogen or an alkyl group.
  • R1 and R2 are the same.
  • R 1 and R 2 may represent an alkylene group, preferably methylene.
  • R1, R2 and R3 are the same.
  • R 1, R 2 and R 3 are identical, they may represent an alkylene group, preferably methylene.
  • X1 and X2 are identical.
  • X1 and X2 may represent a group - PO (OR) (OR ') with R, R' representing independently of one another hydrogen or an alkyl group, preferably -PO3H 2 .
  • X3 comprises at least one -COOH group, for example X3 represents -COOH.
  • the composition comprises at least 0.1 pce inclusive of the compound of formula (I) and / or salts thereof.
  • the composition comprises at most 2 pce inclusive, preferably at most 1 pce inclusive and more preferably at most 0.7 pce inclusive of the compound of formula (I) and / or salt thereof.
  • the scrubbing composition comprises a crosslinking system, more preferably a vulcanization system.
  • the crosslinking system here vulcanization, comprises sulfur donor agents, for example sulfur.
  • the vulcanization system comprises vulcanization activators such as zinc oxide and stearic acid.
  • the vulcanization system comprises an accelerator.
  • the accelerator is chosen from tetrabenzylthiuram disulphide (abbreviated “TBZTD”) and the sulfenamide family consisting of 2-mercaptobenzothiazyl disulfide (abbreviated "MBTS”), N-cyclohexyl-2-benzothiazyl sulfenamide (abbreviated “CBS”), N, N-dicyclohexyl-2-benzothiazyl sulfenamide (abbreviated “DCBS”), N-tert-butyl-2-benzothiazyl sulfenamide (abbreviated as "TBBS”), tert-butyl-2-benzothiazylsulfenimide (abbreviated "TBSI”) and mixtures of these compounds.
  • MBTS 2-mercaptobenzothiazyl disulfide
  • CBS N-cyclohexyl-2-benzothiazyl sulfenamide
  • DCBS N-dic
  • the vulcanization system also comprises a vulcanization retarder such as N- (cyclohexylthio) phthalimide (abbreviated "CTP").
  • a vulcanization retarder such as N- (cyclohexylthio) phthalimide (abbreviated "CTP").
  • the sulfur or sulfur donor agent is used at a preferential rate of between 0.5 and 10 pce inclusive limits, more preferably between 0.5 and 8.0 pce inclusive limits and very preferably between 2.0 and 8.0 pce. terminals included. All accelerators, retarders and vulcanization activators are used at a preferential rate of between 0.5 and 15 pce inclusive. The vulcanization activator (s) is or are used at a preferential rate of between 0.5 and 10 pb inclusive.
  • composition without a compound it is understood that the composition does not include this compound voluntarily introduced into the composition and that this compound, if present, is in the form of traces related for example to the process of manufacture of the compound.
  • composition lacking a compound comprises the latter in an amount less than or equal to 0.1 phr and preferably less than or equal to 0.05 phr.
  • the inner layer CT1 of the monotoron cable gummed in situ C comprises an inner wire 10 and the outer layer of the cable CT3 comprising six outer wires 13 wound helically around the inner wire.
  • the rubber composition is present in each of the capillaries or interstices between the inner wire of the inner layer CT1 and the outer six outer layers of the outer layer CT3.
  • two-layer cables with, for example, three internal wires and nine outer wires.
  • the monotoron cable gummed in situ according to the invention C may comprise an intermediate layer of the cable CT2 comprising N2 intermediate threads.
  • the N2 intermediate son are helically wound around the inner layer CT1 of the cable and the N3 external son of the outer layer CT3 of the cable are helically wound around the intermediate layer CT2 of the cable.
  • the inner layer CT1 comprises an inner wire 10
  • the intermediate layer CT2 comprises six intermediate wires 12
  • the outer layer CT3 comprises twelve outer wires 13.
  • the cables Figures 2 to 4 have a 1 + 6 + 12 structure.
  • the invention is not limited to the configuration illustrated in the Figures 2 to 4 .
  • the inner layer CT1 may comprise more wires, for example two or three wires assembled together (i.e. N1 varies from 1 to 3).
  • the intermediate layer CT2 may comprise five to seven wires (i.e. N2 ranges from 5 to 7).
  • the outer layer CT3 may comprise from ten to fourteen threads (i.e., N3 ranges from 10 to 14).
  • the scrub rubber composition 20 is present in each of the capillaries between the inner wire 10 of the inner layer CT1 and the six intermediate wires 12 of the intermediate layer CT2.
  • such a configuration makes it possible to ensure good protection against corrosion of the internal (s) and intermediate wires.
  • the scrub rubber composition 20 is present in each of the capillaries located between the six intermediate threads 12 of the intermediate layer CT2 and the twelve external threads 13 of the outer layer CT3.
  • such a configuration makes it possible to provide good protection against corrosion of the intermediate and external wires.
  • the scrubbing composition thus makes it possible to form an anticorrosive protection barrier between the core of the cable and the outside.
  • the scrub rubber composition 20 is present in each of the capillaries located between the inner wire 10 of the inner layer CT1 and the six intermediate wires 12 of the intermediate layer CT2 and in each of the capillaries located between the six intermediate threads 12 of the intermediate layer CT2 and the twelve outer threads 13 of the outer layer CT3.
  • such a configuration makes it possible to ensure maximum protection of the various layers of the cable against corrosion.
  • the invention also relates to a multi-strand cable gummed in situ C 'comprising at least one inner layer of the cable CCI and an outer layer of the cable CCE cable.
  • the inner layer of the CCI cable comprises T1 inner strand (s).
  • the outer layer of the CCE cable comprises T2 outer strands wound helically around the inner layer CCI of the cable C '.
  • Each internal and external strand TI TE is a single-strand cable comprising at least an inner layer of the cable CT1 and an outer layer of the cable CT3.
  • the inner layer comprises N1 internal thread (s) and the outer layer comprises N3 outer threads helically wrapped around the inner layer of the cable.
  • each internal strand TI and outer TE is a single strand cable comprises an intermediate layer CT2.
  • the intermediate layer of the cable CT2 comprises N2 intermediate wires wound helically around the inner layer CT1 of the cable, the outer N3 son of the outer layer CT3 of the cable being helically wound around the intermediate layer CT2 of the cable.
  • the multi-strand cables C 'according to the invention are not limited to cables comprising strands of structures represented on the Figures 5 to 10 .
  • each outer strand TE is a monotoron cable gummed in situ according to the invention as described with reference to FIG. figure 4 .
  • each internal strand TI is a monotoron cable gummed in situ according to the invention as described with reference to FIG. figure 4 .
  • each outer strand TE and each inner strand TI is a monotoron cable gummed in situ according to the invention as described with reference to FIG. figure 4 .
  • the rubber scrub composition 20 is the same as previously described for the cables shown.
  • each outer strand TE is a monotoron cable gummed in situ according to the invention as described with reference to FIG. figure 4 the inner strand is a non-gummed strand in situ and a scrub rubber composition comprising a compound of formula (I) or a salt thereof is disposed between the inner layer of the CCI cable and the outer layer of the CCE cable.
  • the scrub rubber composition 20 disposed between the inner layer of the CCI cable and the outer layer of the CCE cable is the same as previously described for the single-rod cables.
  • each outer strand TE and each inner strand TI is a monotoron cable gummed in situ according to the invention and a scrub rubber composition comprising a compound of formula (I) or a salt thereof is disposed between the inner layer of CCI cable and the outer layer of the CCE cable.
  • the scrub rubber composition 20 disposed between the inner layer of the CCI cable and the outer layer of the CCE cable is the same as previously described for the single-rod cables.
  • the strands are monotoron cables not gummed in situ.
  • a scrub rubber composition comprising a compound of formula (I) or a salt thereof is disposed between the inner layer of the CCI cable and the outer layer of the ECC cable.
  • the scrub rubber composition 20 disposed between the inner layer of the CCI cable and the outer layer of the CCE cable is the same as previously described for single-rod cables.
  • the invention also relates to the use of a cable according to the invention for reinforcing articles or semi-finished products made of plastic and / or rubber, for example webs, pipes, belts, conveyor belts, tires, more particularly tires intended for industrial vehicles.
  • the rubber scrub composition 20 is provided in accordance with the general knowledge of those skilled in the art during assembly of the different layers of the cable. Reference is made in particular to publications EP1699973 , WO2006 / 013077 , WO2007 / 090603 , WO09 / 083212 , WO09 / 083213 , WO10 / 012411 , WO10 / 054790 , WO10 / 054791 , WO10 / 112444 , WO10 / 112445 , WO10 / 139583 , WO11 / 000963 , WO11 / 000964 , WO11 / 000950 and WO11 / 000951 .
  • the cable of the invention is particularly intended to be used as reinforcing element for industrial vehicles selected from vans, " heavy goods vehicles” - ie, metros, buses, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles, agricultural or engineering machinery civil, aircraft, other transport or handling vehicles.
  • the cable according to the invention can be used to reinforce different parts of the tires, in particular carcass reinforcement, crown reinforcement of such tires, in particular of industrial tires such as heavy goods vehicles or civil engineering.
  • the invention also relates to these articles or semi-finished products of plastic and / or rubber themselves when reinforced by a cable according to the invention, in particular the tires intended for the industrial vehicles mentioned above. , more particularly heavy-duty tires or civil engineering tires, as well as composite fabrics comprising a matrix of composition of rubber calendering rubber reinforced with an in-situ gummed cable according to the invention, which can be used as carcass or crown reinforcement ply such tires.
  • compositions "Control 1" and “Control 2” and a composition “Invention” as described above were compared.
  • the composition “Control 1” is in accordance with the state of the art known to those skilled in the art, that is to say devoid of corrosion inhibitor.
  • the composition “Control 2” is identical to the composition “Control 1” except that it comprises in addition to glycine.
  • the corrosion inhibitor of the composition "Invention” is in accordance with formula (I). This is in this case N, N-bis (phosphonomethyl) glycine (abbreviated “BPMG”) of formula (II) below and available from Sigma-Aldrich.
  • BPMG N, N-bis (phosphonomethyl) glycine
  • composition "Invention” comprises at least 0.1 pce inclusive and at most 2 pce inclusive, preferably at most 1 pce inclusive and more preferably at most 0.7 pce inclusive of the compound of formula (I) and / or or salts of this compound, here the BPMG.
  • the diene elastomer is natural rubber.
  • the silica is a silica type "HD” - “Zeosil 1165MP” from the company RHODIA.
  • the carbon black is of the N330 type.
  • the antioxidant is N-1,3-dimethylbutyl-N-phenyl-para-phenylenediamine ("Santoflex 6-PPD” from the company FLEXSYS).
  • the organosilane is TESPT ("Si69" from DEGUSSA).
  • the vulcanization accelerator is N-cyclohexyl-2-benzothiazyl sulfenamide (“Santocure CBS” from FLEXSYS).
  • the vulcanization retarder is N- (cyclohexylthio) phthalimide (No. CAS 17796-82-6 ).
  • compositions are manufactured in appropriate mixers, using two successive preparation phases well known to those skilled in the art: a first phase of work or thermomechanical mixing (sometimes called a "non-productive" phase) at high temperature, up to a maximum temperature (denoted Tmax) of between 110 ° C. and 190 ° C., preferably between 130 ° C. and 180 ° C., followed by a second mechanical working phase (sometimes referred to as a "productive" phase) at lower temperature, typically less than 110 ° C, for example between 60 ° C and 100 ° C, finishing phase during which is incorporated the vulcanization system.
  • a first phase of work or thermomechanical mixing (sometimes called a "non-productive" phase) at high temperature, up to a maximum temperature (denoted Tmax) of between 110 ° C. and 190 ° C., preferably between 130 ° C. and 180 ° C.
  • a second mechanical working phase sometimes referred to as a "productive” phase
  • Such phases have been described for example in the
  • the first (non-productive) phase is carried out in a single thermomechanical step during which, in a suitable mixer such as a conventional internal mixer, all the necessary basic constituents are first introduced. (diene elastomer, reinforcing inorganic filler, anti-oxidant, corrosion inhibitor and coupling agent), then in a second step, for example after one to two minutes of mixing, any additional processing agents and other various additives, with the exception of the vulcanization system.
  • a suitable mixer such as a conventional internal mixer
  • the necessary basic constituents are first introduced.
  • a suitable mixer such as a conventional internal mixer
  • the necessary basic constituents are first introduced.
  • a suitable mixer such as a conventional internal mixer
  • thermomechanical work step may be added to this internal mixer, after the mixture has fallen and intermediate cooling (cooling temperature preferably below 100 ° C.), in order to subject the compositions to a complementary thermomechanical treatment, in particular to improve still further, the dispersion in the elastomeric matrix of the reinforcing inorganic filler and its coupling agent.
  • the total mixing time, in this non-productive phase, is preferably between 2 and 10 minutes.
  • the vulcanization system is incorporated at low temperature, generally in an external mixer such as a roll mill; the whole is then mixed (productive phase) for a few minutes, for example between 5 and 15 minutes.
  • the final composition thus obtained is then calendered, for example in the form of a sheet, a plate or extruded, for example to form a rubber profile.
  • the vulcanization (or cooking) is conducted in a known manner at a temperature generally between 130 ° C and 200 ° C, preferably under pressure, for a sufficient time which may vary for example between 5 and 90 min depending in particular on the temperature cooking, the vulcanization system adopted, the vulcanization kinetics of the composition in question or the size of the tire.
  • a tear test is carried out according to ASTM D2229 on test pieces comprising 2.30NF structural metal cables, a portion of which is interposed between two strips made in the prepared rubber composition and another portion is left free.
  • the force required to pull the cable from the two rubber bands is measured. The measurement is made for 15 cables. The value used is the average of the measurements on these 15 cables. The higher the value of the force, the greater the adhesion between the cable and the rubber composition.
  • the adhesion test described above is carried out with vulcanized and / or aged test pieces under different conditions A, B, C and D.
  • Condition A normal cooking corresponds to a test carried out on a test piece baked for less than 1 hour at a temperature above 100 ° C.
  • Condition B (wet wet aging) corresponds to a test carried out on a specimen comprising the raw composition and aged for several days at a temperature above 30 ° C and at more than 50% relative humidity.
  • Condition C aging in a corrosive atmosphere corresponds to a test carried out on a specimen comprising the raw composition and aged for several days in an NaCl solution.
  • Condition D (wet wet aging) corresponds to a test carried out on a test piece baked for less than 1 hour at a temperature above 100 ° C. and aged for several days at a temperature above 30 ° C. and at more than 50% relative humidity.
  • composition "Invention” has adhesion performance at least equivalent to the "Control 1" composition of the state of the art regardless of the test conditions except in conditions C (aging in a corrosive atmosphere) and D (wet aging). baked), conditions for which the composition “Invention” has adhesion properties greater than those of the composition "Control 1" of the state of the art.
  • the composition “Invention” thus makes it possible to inhibit the corrosion created by the corrosive agents.
  • the "Control 2" composition is not effective against corrosion.
  • Mooney plasticity is achieved using a consistometer according to ASTM D 1646-99. Mooney plasticity measurement is carried out according to the following principle: the generally raw mixture is molded in a cylindrical chamber heated to a given temperature, usually 100 ° C and here 60 ° C. After a minute of preheating, a type L rotor rotates within the test tube at 2 revolutions per minute and the useful torque is measured to maintain this movement after 4 minutes of rotation.
  • certain wires could be of non-circular section, for example plastically deformed, in particular with a substantially oval or polygonal cross-section, for example triangular, square or rectangular.
  • the son of circular section or not, for example a corrugated wire, may be twisted, twisted helical or zig-zag.
  • the diameter of the wire represents the diameter of the cylinder of imaginary revolution which surrounds the wire (space diameter), and no longer the diameter (or any other transverse size, if its section is not circular) of the core wire itself.
  • linear son that is to say right, and conventional circular cross section.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Ropes Or Cables (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)
  • Flexible Shafts (AREA)

Claims (15)

  1. In situ gummiertes einlitziges Seil (C), umfassend:
    - eine Seil-Innenschicht (CT1) mit N1 inneren Drähten,
    - eine Seil-Außenschicht (CT3) mit N3 äußeren Drähten, die spiralförmig um die Seil-Innenschicht gewickelt sind,
    - eine Kautschukzusammensetzung (20), die zwischen der Seil-Innenschicht und der Seil-Außenschicht angeordnet ist,
    dadurch gekennzeichnet, dass die Kautschukzusammensetzung (20) eine Verbindung mit der Formel (I) oder ein Salz dieser Verbindung umfasst:
    Figure imgb0012
     wobei
    - jede Gruppe R1, R2, R3 unabhängig voneinander für eine Alkylen-, Arylen-, Arylalkylen-, Alkylarylen- oder Cycloalkylengruppe steht,
    - jede Gruppe X1, X2 unabhängig voneinander für - COOH, -CO-NH-OH, -SOOH, -PO(OR)(R') oder -PO(OR)(OR') steht, wobei R, R' unabhängig voneinander für Wasserstoff oder eine Alkylgruppe stehen, und
    - X3 mindestens eine Gruppe -COOH, -CO-NH-OH, -SOOH, -PO(OR)(R') oder -PO(OR)(OR') umfasst, wobei R, R' unabhängig voneinander für Wasserstoff oder eine Alkylgruppe stehen.
  2. In situ gummiertes einlitziges Seil (C) nach dem vorhergehenden Anspruch, wobei X3 für -COOH, -CO-NH-OH, -SOOH, -PO(OR)(R') oder -PO(OR)(OR') steht, wobei R, R' unabhängig voneinander für Wasserstoff oder eine Alkylgruppe stehen.
  3. In situ gummiertes einlitziges Seil (C) nach Anspruch 1 oder 2, wobei R1=R2.
  4. In situ gummiertes einlitziges Seil (C) nach dem vorhergehenden Anspruch, wobei R1 und R2 für eine Alkylengruppe, vorzugsweise Methylen, stehen.
  5. In situ gummiertes einlitziges Seil (C) nach einem der vorhergehenden Ansprüche, wobei R1=R2=R3.
  6. In situ gummiertes einlitziges Seil (C) nach dem vorhergehenden Anspruch, wobei R1, R2 und R3 für eine Alkylengruppe, vorzugsweise Methylen, stehen.
  7. In situ gummiertes einlitziges Seil (C) nach einem der vorhergehenden Ansprüche, wobei X1=X2.
  8. In situ gummiertes einlitziges Seil (C) nach dem vorhergehenden Anspruch, wobei X1 und X2 für eine Gruppe -PO(OR)(OR') stehen, wobei R, R' unabhängig voneinander für Wasserstoff oder eine Alkylgruppe, vorzugsweise -PO3H, stehen.
  9. In situ gummiertes einlitziges Seil (C) nach einem der vorhergehenden Ansprüche, wobei X3 mindestens eine Gruppe -COOH umfasst.
  10. In situ gummiertes einlitziges Seil (C) nach dem vorhergehenden Anspruch, wobei X3 für -COOH steht.
  11. In situ gummiertes mehrlitziges Seil (C'), dadurch gekennzeichnet, dass es mindestens eine Litze umfasst, die ein in situ gummiertes einlitziges Seil (C) nach einem der vorhergehenden Ansprüche ist.
  12. In situ gummiertes mehrlitziges Seil (C') nach dem vorhergehenden Anspruch, umfassend:
    - eine Seil-Innenschicht (CCI) mit T1 inneren Litzen (TI),
    - eine Seil-Außenschicht (CCE) mit T2 äußeren Litzen (TE), die spiralförmig um die Seil-Innenschicht (CCI) gewickelt sind,
    - wobei mindestens eine der inneren und/oder äußeren Litzen ein in situ gummiertes einlitziges Seil nach einem der Ansprüche 1 bis 10 ist.
  13. In situ gummiertes mehrlitziges Seil (C') nach dem vorhergehenden Anspruch, das eine Kautschukzusammensetzung umfasst, die zwischen der Innenschicht (CCI) aus den T1 inneren Litzen (TI) des Seils und der Außenschicht (CCE) aus den T2 äußeren Litzen (TE) des Seils angeordnet ist, wobei die Kautschukzusammensetzung (20) eine Verbindung mit der Formel (I) umfasst:
    Figure imgb0013
     wobei
    - jede Gruppe R1, R2, R3 unabhängig voneinander für eine Alkylen-, Arylen-, Arylalkylen-, Alkylarylen- oder Cycloalkylengruppe steht,
    - jede Gruppe X1, X2 unabhängig voneinander für - COOH, -CO-NH-OH, -SOOH, -PO(OR)(R') oder -PO(OR)(OR') steht, wobei R, R' unabhängig voneinander für Wasserstoff oder eine Alkylgruppe stehen, und
    - X3 mindestens eine Gruppe -COOH, -CO-NH-OH, -SOOH, -PO(OR)(R') oder -PO(OR)(OR') umfasst, wobei R, R' unabhängig voneinander für Wasserstoff oder eine Alkylgruppe stehen.
  14. In situ gummiertes mehrlitziges Seil (C'), dadurch gekennzeichnet, dass es Folgendes umfasst:
    - eine Seil-Innenschicht (CCI) mit T1 inneren Litzen (TI),
    - eine Seil-Außenschicht (CCE) mit T2 äußeren Litzen (TE), die spiralförmig um die Seil-Innenschicht (CCI) gewickelt sind,
    - eine Kautschukzusammensetzung (20), die zwischen der Innenschicht (CCI) des Seils und der Außenschicht (CCE) des Seils angeordnet ist, wobei die Kautschukzusammensetzung eine Verbindung mit der Formel (I) oder ein Salz dieser Verbindung umfasst:
    Figure imgb0014
     wobei
    - jede Gruppe R1, R2, R3 unabhängig voneinander für eine Alkylen-, Arylen-, Arylalkylen-, Alkylarylen- oder Cycloalkylengruppe steht,
    - jede Gruppe X1, X2 unabhängig voneinander für - COOH, -CO-NH-OH, -SOOH, -PO(OR)(R') oder -PO(OR)(OR') steht, wobei R, R' unabhängig voneinander für Wasserstoff oder eine Alkylgruppe stehen, und
    - X3 mindestens eine Gruppe -COOH, -CO-NH-OH, -SOOH, -PO(OR)(R') oder -PO(OR)(OR') umfasst, wobei R, R' unabhängig voneinander für Wasserstoff oder eine Alkylgruppe stehen.
  15. Reifen, der ein in situ gummiertes einlitziges Seil (C) nach einem der Ansprüche 1 bis 10 oder ein in situ gummiertes mehrlitziges Seil (C') nach einem der Ansprüche 11 bis 14 umfasst.
EP15731535.9A 2014-06-12 2015-06-11 In-situ-gummiertes kabel mit einer gummierzusammensetzung mit einem korrosionsinhibitor Active EP3155167B1 (de)

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FR1455343A FR3022261B1 (fr) 2014-06-12 2014-06-12 Cable gomme in situ comprenant une composition de gommage comprenant un inhibiteur de corrosion
PCT/EP2015/063017 WO2015189313A2 (fr) 2014-06-12 2015-06-11 Câble gommé in situ comprenant une composition de gommage comprenant un inhibiteur de corrosion

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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3103201A1 (fr) * 2019-11-15 2021-05-21 Compagnie Generale Des Etablissements Michelin Câble multi-torons à deux couches avec couche interne gainée à rendement amélioré
CN112012031B (zh) * 2020-08-21 2021-08-03 安徽力鸿新材料科技有限公司 一种用于制作抛丸线的硬质不锈钢丝及其加工工艺

Family Cites Families (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2673187B1 (fr) 1991-02-25 1994-07-01 Michelin & Cie Composition de caoutchouc et enveloppes de pneumatiques a base de ladite composition.
US5139874A (en) * 1991-09-05 1992-08-18 The Goodyear Tire & Rubber Company Cable for reinforcing rubber articles
JP2709872B2 (ja) * 1991-12-27 1998-02-04 横浜ゴム株式会社 鋼線補強高圧ゴムホース
CA2109904C (en) * 1992-12-18 2004-09-14 Pol Bruyneel Multi-strand steel cord
FR2732351B1 (fr) 1995-03-29 1998-08-21 Michelin & Cie Composition de caoutchouc pour enveloppe de pneumatique renfermant de la silice dopee aluminium a titre de charge renforcante
JP4157608B2 (ja) * 1996-06-26 2008-10-01 株式会社ブリヂストン ゴム組成物
AU5161699A (en) 1998-07-22 2000-02-14 Michelin Recherche Et Technique S.A. Coupling system (white filler/diene elastomer) based on polysulphide alkoxysilane, zinc dithiophosphate and guanidine derivative
EP1115785B1 (de) * 1998-07-22 2002-10-09 Société de Technologie Michelin Haftvermittlerzusammensetzung (weisser füllstoff/dienrubber) die ein alkoxysilanpolysulfid, ein enamin und ein guanidinderivat enthält
FR2823215B1 (fr) 2001-04-10 2005-04-08 Michelin Soc Tech Pneumatique et bande de roulement de pneumatique comportant a titre d'agent de couplage un tetrasulfure de bis-alkoxysilane
BR0211898A (pt) 2001-08-13 2004-09-21 Michelin Soc Tech Composição de borracha diênica para pneumático, processo para preparar a mesma, utilização de uma composição de borracha, artigo semi-acabado de borracha para pneumático, pneumático, banda de rodagem de pneumático, e, processo para reforçar uma composição de borracha diênica destinada à fabricação de pneumáticos
US7799856B2 (en) * 2001-10-05 2010-09-21 Bridgestone Corporation Rubber composition
FR2840908B1 (fr) * 2002-06-12 2005-02-18 Michelin Soc Tech Composition de caoutchouc comprenant un sel de thiouronium, son procede de preparation, pneumatique a base d'une telle composition et utilisation a titre d'agent anti-reversion d'un sel de thiouronium
DE10328919B4 (de) * 2003-06-26 2007-01-04 Klaus Bloch Textiler Faden
FR2864556B1 (fr) * 2003-12-24 2006-02-24 Michelin Soc Tech Cable a couches pour armature de carcasse de pneumatique
JP2005307368A (ja) * 2004-04-19 2005-11-04 Yokohama Rubber Co Ltd:The スチールコード及びそれを用いた空気入りラジアルタイヤ
FR2873721A1 (fr) * 2004-08-02 2006-02-03 Michelin Soc Tech Cable a couches pour armature de sommet de pneumatique
FR2897076B1 (fr) 2006-02-09 2008-04-18 Michelin Soc Tech Cable composite elastique pour pneumatique.
JP4909688B2 (ja) * 2006-09-08 2012-04-04 株式会社ブリヂストン ゴム複合体及びそれを用いたタイヤ
FR2925923B1 (fr) 2007-12-28 2009-12-18 Michelin Soc Tech Procede et dispositif de fabrication d'un cable a deux couches du type gomme in situ
FR2925922B1 (fr) 2007-12-28 2009-12-18 Soc Tech Michelin Cable a couches pour ceinture de pneumatique
FR2934614B1 (fr) 2008-08-01 2010-09-10 Michelin Soc Tech Cable a couches gomme in situ pour armature carcasse de pneumatique.
FR2938557B1 (fr) 2008-11-17 2011-02-18 Michelin Soc Tech Cable a trois couches, gomme in situ, pour armature de carcasse de pneumatique
FR2938558B1 (fr) 2008-11-17 2010-12-31 Michelin Soc Tech Procede et dispositif de fabrication d'un cable a trois couches du type gomme in situ.
FR2943691B1 (fr) 2009-03-31 2011-08-19 Michelin Soc Tech Procede et dispositif de fabrication d'un cable a trois couches du type gomme in situ
FR2943690B1 (fr) 2009-03-31 2011-08-19 Michelin Soc Tech Procede et dispositif de fabrication d'un cable a trois couches du type gomme un situ
JP5513002B2 (ja) * 2009-04-20 2014-06-04 株式会社ブリヂストン ゴム−スチールコード複合体および空気入りラジアルタイヤ
FR2946366B1 (fr) 2009-06-03 2011-12-02 Michelin Soc Tech Cable a trois couches,gomme in situ,pour armature carcasse de pneumatique.
FR2947574B1 (fr) 2009-07-03 2012-11-09 Michelin Soc Tech Cable multitorons dont les torons elementaires sont des cables a deux couches gommes in situ.
FR2947577B1 (fr) 2009-07-03 2013-02-22 Michelin Soc Tech Cable metallique a trois couches gomme in situ de construction 3+m+n
FR2947576B1 (fr) 2009-07-03 2011-08-19 Michelin Soc Tech Cable metallique a trois couches gomme in situ de construction 2+m+n
FR2947575B1 (fr) 2009-07-03 2011-08-19 Michelin Soc Tech Cable multitorons dont les torons elementaires sont des cables a deux couches gommes in situ.
JP5645422B2 (ja) 2010-02-23 2014-12-24 地方独立行政法人 大阪市立工業研究所 銅−亜鉛合金電気めっき液
DE102011007010B4 (de) * 2010-04-23 2017-04-06 The Yokohama Rubber Co., Ltd. Gummi-Metal-Verbundstoff, vulkanisiertes Produkt davon und dessen Verwendung in einem Luftreifen
FR2974100B1 (fr) * 2011-04-14 2014-08-22 Michelin Soc Tech Composition de caoutchouc comprenant un derive du thiophene
US9186933B2 (en) * 2012-10-12 2015-11-17 The Goodyear Tire & Rubber Company Functionalized polymer, rubber composition and pneumatic tire

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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WO2015189313A3 (fr) 2016-02-11
US10378148B2 (en) 2019-08-13
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CN106661829A (zh) 2017-05-10
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FR3022261B1 (fr) 2016-06-03
JP6419854B2 (ja) 2018-11-07
CN106661829B (zh) 2019-01-15
EP3155167A2 (de) 2017-04-19
US20170107663A1 (en) 2017-04-20

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